Carbon dioxide adsorption on a ZnO(100) substrate studied by infrared reflection absorption spectroscopy

Abstract

The adsorption of carbon dioxide on the mixed-terminated ZnO(100) surface of a bulk single crystal was studied by UHV Infrared Reflection Absorption Spectroscopy (IRRAS). In contrast to metals, the classic surface selection rule for IRRAS does not apply to bulk oxide crystals, and hence vibrational bands can also be observed for s-polarized light. Although this fact substantially complicates data interpretation, a careful analysis allows for a direct determination of the adsorbate geometry. Here, we demonstrate the huge potential of IR-spectroscopy for investigations on oxide single crystal surfaces by considering all three components of the incident polarized light separately. We find that the tridentate (surface) carbonate is aligned along the [0001] direction. A comparison to data reported previously for CO₂ adsorbed on the surfaces of ZnO nanoparticles provides important insight into the role of defects in the surface chemistry of powder particles.